Two step reaction of textile fibers with 2-vinylsulfonylethanol



United States Patent 3,512,916 TWO STEP REACTION OF TEXTILE FIBERS WITH Z-VINYLSULFONYLETHANOL Harlan B. Freyermuth, Easton, Pa., and David I. Randall, New Vernon, N.J., assignors to GAF Corporation, a corporation of Delaware No Drawing. Filed Oct. 6, 1961, Ser. No. 143,304 Int. Cl. D06p 5/00; D06m 9/14, 13/30 U.S. Cl. 8-17 8 Claims ABSTRACT OF THE DISCLOSURE Modification of fibrous materials containing reactive groups with 2-vinylsulfonylethanol. The materials may be mechanically deformed, dyed and/or treated with discoloration inhibiting boron containing compounds during the modification.

This invention relates to a method for improving the properties of fibrous material, and more particularly to a method for improving (i.e. increasing, rendering more permanent, etc.) dimensional and shape retention properties variously referred to as wet and/or dry crease resistance, crease angle retention, crease recovery, wrinkle resistance, wrinkle recovery, dimensional stability, wash-and-wearability, swelling resistance, shrinkage resistance, tensile strength, retention of creases, pleats, glazed, embossed and other mechanical defects, and the like, in addition to other properties such as resistance to attack by moths, mildew and the like, washing, laundry bleaches and sours, chlorine retention, industrial gases and other environmental conditions, development of objectionable odors, yellowing or other discoloration, hydrolysis, heat and/ or abrasion and the like. The invention also relates to improved fibrous material produced by such method.

Crease resistant finishing agents for fibrous material, particularly cellulosic material such as cotton, have recently become very popular and a large proportion of such material now provided to the trade have been treated with such agents for the production of so called wash and wear effects and the like. Most such agents have up to the present been resinous, which involves a number of disadvantages including unduly high costs, a tendency to stiffen and otherwise undesirably change the character and properties of the fibrous material and the like. Further, considerable room for improvement of such agents remains with respect to other fiber properties of the type referred to above.

In U.S. 2,524,399 there is disclosed a shrink-proofing and crease-proofing process involving the reaction of cel: lulose fibers with divinyl sulfone in an aqueous alkaline medium. Although this process is considered to be nonresinous, thereby eliminating some of the aforementioned disadvantages, it is subject to a number of other objections which have prevented its commercial adoption. The most important objection to this process resides in the fact that divinyl sulfone is a very active skin vesicant and lachrymator whereby its use in commerical operations, even with costly specialized equipment, is extremely hazardous. Another objection to this patented process is its failure to produce any substantial improvements in dry crease resistance of the treated cellulose fibers.

A recently developed shrink-proofing and crease-proofing'process which is highly successful and in wide commercial use involves treatment of fibrous material with 2,2'-sul fonyldiethanol in the presence of an aqueous alkaline medium followed by drying and curing the treated fibrous material at an elevated temperature. In this process, which eliminates toxicity hazards and yields fibrous Patented May 19, 1970 material having surprisingly improved properties with respect to both wet and dry crease resistance, no reaction takes place during the initial treatment of the fibrous material in the aqueous alkaline medium, the cross-linking between the fibrous material and the 2,2'-sulfonyldiethanol taking place during the subsequent curing step. While this process is highly satisfactory for most purposes, it has certain limitations in that the resulting cross-linked fibrous material is resistant to subsequent dyeing and mechanical deformation. It is thus difficult to impart to the cross-linked product permanent creases, colors, and the like.

It is an object of this invention to provide a process for improving the properties of fibrous material which will not be subject to one or more of the above disadvantages. Another object of this invention is the provision of such a process which simultaneously provides the fibrous material with permanently fixed finishing agents and the like. Still another object of this invention is the provision of improved fibrous material produced by such a process. Other objects and advantages will appear as the description proceeds.

The attainment of the above objects is made possible by this invention which comprises reacting fibrous material With 2-vinylsulfonylethanol in the presence of an aqueous alkaline medium and subsequently curing the resulting fibrous material at a temperature of at least about 220 F. During the initial treatment of the fibrous material with this compound in the presence of an aqueous alkaline medium, which may be carried out at any temperature such as from room temperature up to the boiling point of the medium, the compound monofunctionally reacts through the vinyl group therein with a reactive situs in the fibrous material such as a hydroxy group in cellulose fiber. This monofunctionally reacted fibrous material containing a hydroxyethylsulfonylethyl group may, in the case of cellulose for example, be represented by the formula Other reacted fibers of different chemical constitution may be represented by the formula wherein X represents 0, NR, S, etc., R is H, lower alkyl or other substituent, and n is one or zero (for example by direct addition to a reactive methylene linkage in the fiber molecule chain).

This initial monofunctional reaction product of the fiber with the 2-vinylsulfonylethanol is not cross-linked and has substantially no better dry crease resistance than the original fiber, although it shows a noticeable improvement in wet crease resistance. Nor has it acquired any substantially increased resistance to wet treatments or treatments with any one of a number of non-functional agents such as dyes, brighteners, antistatic agents, softeners, etc. It is accordingly a feature of this invention that this initial reaction product may be subjected to any desired intermediate chemical and/or mechanical treatments whereafter the fiber or fabric may be fixed and dimensionally stabilized in any desired permanent shape configuration by curing at elevated temperatures in the presence of an alkaline catalyst. During this subsequent curing step, the fibers are cross-linked by reaction between the free hydroxyethylsulfonylethyl group in the initially reacted product of the above formula and a reactive situs of an adjacent molecule. The cross-linked fibrous material may accordingly be represented by the following formulae The ability to apply such intermediate treatments to the initially reacted fibrous material is obviously advantageous. The fiber, cloth or piece goods may, after being initially reacted with the 2-vinylsulfonylethanol in the presence of an aqueous alkaline medium, be treated with dyes and other chemicals and functional agents, fabricated, sewed, fashioned, creased, pleated, etc. in normal manner, after which the dyes, chemicals or other functional agents applied in such treatments and any mechanical deformations such as hems, pleats, creases and the like may be permanently fixed in the fibrous material by heat treatment as described to cross-link the fibers in the desired permanent shape configuration.

If desired, the process may of course be carried out continuously and without intermediate treatments, for the sole purpose of providing improvements in dimensional and shape retention properties by directly drying and curing the fibrous material after its initial reaction with the 2- vinylsulfonylethanol in the presence of an aqueous alkaline medium. In this embodiment, it is preferred to omit a washing step after the initial treatment to assure maximum use of any 2-vinylsnlfonylethanol which may not yet have reacted with the fiber in the presence of the aqueous alkaline medium or which may have homopolymerized or cyclized. Such unreacted 2-vinylsulfonylethanol, and fission products of such homopolymers and cyclized products will also react and cross-link the fibers during the subsequent curing step.

The 2-vinylsulfonylethanol employed employed in the present process, and methods for its production are disclosed and claimed in the copending application of Prey ermuth, Ser. No. 143,303 (E-1520) filed on Oct. 6, 1961. This compound is a water soluble oil at room temperature and is devoid of vesicant, lachrymator and other toxic properties whereby it may be readily adapted for commercial use.

In carrying out the process of this invention, the 2-vinylsulfonylethanol is applied to the fibrous material in the form of an aqueous solution thereof at any temperature ranging from room temperature to the boiling point of the solution. This solution is rendered alkaline by the presence or addition of any suitable alkaline reacting substance, preferably alkali metal (sodium, potassium, lith ium, etc.) hydroxide, carbonate, bicarbonate, phosphate, silicate, borate, acetate or the like, or an organic base such as triethanolamine or the like in an amount sufficient to yield a pH of about 7.5 to 10.5 or more. Such amount may range from less than 0.5% up to or more in the solution. The alkali metal hydroxides are preferred, particularly sodium hydroxide, since this substance has been found to yield superior results with respect to promotion of the initial reaction between the 2-vinylsulfonylethanol and the fibrous material in the presence of an aqueous medium. Other alkaline reacting substances may be employed including sodium sulfide, dipotassium tartrate, disodium phthalate and the like.

Instead of including the alkaline reacting substance in the solution of 2-vinylsulfonylethanol, it is in some in stances desirable to minimize homopolymerization, cyclization and the like by applying the alkaline substance in any desired manner as by spraying, padding, or the like, to the fibrous material prior to its treatment with the solution containing the 2-viny1sulfonylethanol, or to the fibrous material previously treated with and carrying the 2-vinylsulfonylethanol.

The concentration of the 2-vinylsulfonylethanol in the treating medium is not particularly critical and may range from about 0.5 to 60% or more depending upon the manner of application to the fibrous material, the character of the fibrous material, the properties desired, and the like. The aqueous medium containing the 2-vinylsulfonylethanol may be applied to the fibrous material by immersion, padding, spraying, printing, or any other desired manner, continuously or otherwise. For overall effects, it is preferred to apply an excess of the aqueous alkaline medium containing the Z-vinylsulfonylethanol followed by a squeezing step with a liquor pickup of about 30% or less to or more by weight of the fiber. For printing or other decorative purposes, the aqueous solution of 2-vinylsulfonylethanol may be appropriately thickened in known manner. In general, optimum dimensional and shape retention properties are obtained by so conducting the proc ess as to provide the fibrous material with about 1 to 12% of combined 2-vinylsulfonylethanol by weight of the material. In this respect, adjustment of the initial concentra tion and/or amount of 2-vinylsulfonylethanol applied to the fibrous material must be made to compensate for any amounts of the Z-vinylsulfonylethanol lost due to homopolymerization, cyclization and the like, which in some instances may constitute up to 50% or more of the amount added to the initial treating solution.

Following application of the 2-vinylsulfonylethanol to the fibrous material in the presence of the aqueous alkaline medium, the treated material may be squeezed and directly dried and cured or may be subjected to any desired chemical and mechanical treatments prior to the curing step, with optional washing steps at any stage of the process. Preferably, the treated and squeezed material is allowed to remain without further treatment for a period of time which may range from less than 5 minutes up to two hours or more to permit the initial reaction to be completed. This may be accomplished in any desired manner as for example by rolling the impregnated fibrous material in a waterproof wrapper or other means during this extended period.

As previously disclosed, the initial reaction product of the fibrous material with the 2-vinylsulfonylethanol may be subjected to treatment with any desired chemical agents, including dyestuffs ordinarily employed for treating or coloring the fibrous material and the like, since the afiinity for such dyestuffs and chemicals is substantially undiminished by such reaction. Similarly, the initial reaction product is amenable to mechanical operations of the above described type and the like since no cross-linking has yet taken place in the material.

The curing step for completing the desired cross-linking reaction must be carried out in the presence of an alkaline catalyst. Accordingly, if the initially reacted fibrous material has been washed and/or otherwise subjected to intermediate wet treatments whereby the alkaline substances applied to the fibrous material with the 2-vinylsulfonylethanol are no longer present, the initially reacted fibrous material must be again treated with an alkaline reacting substance of similar type and in similar proportions immediately prior to curing the material. In such repeated treatment with an alkaline reacting substance, the alkali metal carbonates, particularly sodium carbonate, are preferred for optimum results with respect to promotion of the cross-linking rection and diminution of tendering of the fibrous material by the high curing temperatures required. The curing step is carried out at a temperature of at least about 220 F. and preferably at least about 240 F. The duration of the curing step will generally vary inversely with the temperature, althoughof course both temperature and duration will depend upon the type of fiber being treated, the results desired, etc. In general, the curing step will usually range up to 10 minutes or more at 220 F. to as little as 15 seconds or less at 475 to 500 F. Too high a curing temperature and/or duration causes fiber damage and is to be avoided. The optimum curing temperature and duration may be readily determined by routine experimentation in any particular instance.

Following the curing step, the treated fibrous material may be simply washed and/or bleached in known manner with the usual oxidizing agents such as sodium hypochlorite, hydrogen peroxide or the like. For white materials, it is usually desirable to apply a bleaching treatment to the cured fibrous materials directly or, if desired, after an intermediate washing. Such bleaching is also often desirable when treating previously dyed fibrous material since the curing step may darken, dull or discolor the shade of the dyeing. As a corollary, dyestuffs applied during the aforementioned operations intermediate the initial monofunctional reaction and the final curing should be resistant to alkaline curing at the above temperatures, and to the above bleaching agents.

The above mentioned discoloration, darkening, or dulling tendencies of the alkaline curing step are particularly troublesome in the processing of white fibrous material, and may be minimized or eliminated by including in the last alkaline treatment of the fibrous material preceding the curing step a boron-containing compound as disclosed and claimed in the copending application of Freyermuth and Mayhew, Ser. No. 96,704, filed Mar. 20, 1961.

The mechanism by which such boron-containing compounds function to reduce discoloration is diflicult to postulate in view of the fact that perborate compounds are considered to have an oxidizing effect, alkali metal borohydrides are reducing agents, and alkali metal tetraborates such as borax are neither. The nature of the boron-containing compound employed to reduce discoloration is accordingly relatively immaterial. Thus, there may be employed boric acid and fluoroboric acid and their metal, ammonium and amine salts, and boron fluoride addition products with such compounds as diethyl ether, water, lower alcohols such as methanol, ethanol, propanol, and the like, ammonia, aliphatic and aromatic amines such as ethylamine, aniline and the like, carboxylic acids such as acetic, propionic, stearic and benzoic and the like, amides such as acetamide, propionamide and the like, and phenols, thiophenols, cresols, naphthols, and the like.

, A preferred group of boron-containing compounds operative herein are the ammonium, amine and metal (in cluding also alkaline earth metal and alkali metal) borates such as the metaborates, perborates, and tetraborates. The alkali metal borates such as those of sodium and potassium are preferred because of their economy, availability, solubility properties, etc. Other such operative boron-containing compounds are the borates of amines such as mono-, diand tri-methylarnine, -ethylamine-, propylamine, -butylamine, -octylamine, -cyclohexylamine, mono-, di-, and triethanolamine, -proparlamine, -butanolamine, and -octanolamine, aromatic amines such as benzylamine, heterocyclic amines such as morpholine, piperidine, pyridine, and the like, and metals such as calcium, magnesium, zinc, manganese, aluminum, barium, copper, iron, nickel, tin, and the like.

Another preferred group of boron-containing compounds are the borohydrides of the same cations as referred to in the preceding paragraph with respect to the borates. Those preferred are the alkali metal borohydrides, particularly sodium borohydride.

The above described boron-containing compound is applied to the fibrous material in an amount suflicient to obtain the desired reduction in discoloration, which amount will be readily ascertainable in any particular instance by routine experimentation. Usually,.an aqueous medium containing about 0.03 to 5% of the boron-com taining compound will sufi'ice in most instances. The borohydrides are extremely effective in relatively small amounts in the lower part of the aforementioned range and may be employed in concentrations of about 0.03 to 0.08%. The borates are generally employed in higher concentrations of about 0.1 to 5%, preferably about 0.1 to 1%.

The present process may also advantageously be employed for simultaneously dyeing the fibrous material with a reactive dyestuff. Such dyestuffs may be of any type, inorganic but generally organic, containing a reactive atom or group, capable of reacting with the fiber being treated in the above described aqueous alkaline treating medium and/or in the subsequent heat curing step. As examples of classes of such reactive dyestuffs, which may be nit'ro dyestuffs, dyestuffs of the azo, anthraquinone, phthalocyanine or any other series, including inorganic, which dyestuffs may be metal free or may contain metal in complex union, there may be mentioned dyestuffs containing an s-triazinyl radical carrying one or two chlorine or bromine atoms directly attached to the triazine ring, dyestuffs containing a pyrimidyl radical carrying one or two chlorine or bromine atoms directly attached to the pyrimidine ring and dyestuffs containing a B-halogenopropionyl, fi-haloethylsulfonyl, fi-halogenoethylsulfamyl, B-sulfatoethylsulfonyl, B-phosphatoethylsulfonyl, fi-acyloxyethylsulfonyl, fl-hydroxyethylsulfonyl, chloroacetylamine, ,3 (chloromethyl)-,3-sulfatoethylsulfamyl, vinyl sulfone, alkyl phosphite, or sulphonfluoride radical. Such radicals particularly those containing a sulphonyl group, may if desired be nuclearly substituted either directly to the sulfonyl group or through a methylene or other linkage. Specific examples of such dyestuffs are described in British No. 209,723 in Examples 1 and 2, British No. 298,484 in Example 1, British Nos. 456,343, 460,224, 733,471, 740,533, 775,308, 772,030, 774,925, 780,591, 81,930, 85,120, and 785,222, French Nos. 901,187, and 907,103, Belgium Nos. 497,065, 543,214, 543,215, 543,216 and US. Nos. 1,935,929, 2,151,857, 2,424,493, 2,434,150, 2,657,205, 2,670,265, 2,728,762, 2,743,267, 2,766,231, 2,784,204, etc. US. 2,895,785 also discloses methods for dyeing textiles with reactive dyestufis followed by an alkaline heating step.

For simultaneously dyeing the fibrou material as described above, a suitable amount of reactive dyestuffs may be included in the above described aqueous medium containing the 2-vinylsulfonylethanol and/or alkaline substance and the process otherwise carried out unchanged. The concentration of reactive dyestulf to be included in the aqueous medium is of course a matter of choice obvious to skilled dyers, and may range from about 0.05 to 2 or 3% in the aqueous medium depending upon the dyestuff, the shade desired, etc. Alternatively, the reactive dyestuff may of course be applied to the fibrous material after the initial reaction with the 2-vinylsulfonylethanol and before the alkaline curing step.

Most effective reaction and cross-linking of the 2-vinylsulfonylethanol occurs with hydroxy groups in fibrous material such as cellulose, polyvinyl alcohol, partially hydrolyzed polyvinyl acetate and cellulose acetate and the like. Reaction also occurs with other fibers containing reactive or replaceable atoms or groups such as hydrogen or halogen or the like, or with fibers containing unsaturated linkages.

The process of this invention has been found to be high ly effective for improving the properties of cellulosic fibers of natural or synthetic type such as cotton, linen, wood, paper, regenerated cellulose and the like. The fibrous material may be in any of the usual forms and in natural bulk, interwoven, knitted, or felted form as for example in the form of staple fiber or continuous filaments in bulk form or in the form of tow, rope, yarns, slubbings, warps, fabrics, felts, and the like, and treated as a wound package, running length, fibrous stock, bulk, etc. In addition to cellulose and its derivatives, the process of this invention may be employed for improving other fibers, including natural and synthetic proteinaceous fibers such as wool, silk, leather, animal hides and skins, casein, and zein, polyamides such as nylon and polypyrrolidone, polyurethanes, polyesters, copolymers or homopolymers containing recurring carboxylic or cyano groups, polyvinyl alcohol, partially hydrolyzed cellulose acetate and polyvinyl acetate, polyvinyl chloride, and mixtures, copolymers and graft polymers thereof. Mixed fabrics and fibers may likewise be so treated. The process of the present invention finds its greatest advantage in the treatment of white felts and woven fabrics, particularly cotton shitting, sheetwear, apparel, and the like. When employed for simultaneously dyeing the material, brighter, truer and faster shades of dyeings are obtainable. When applied to previously dyed or pigmented material, improved fastness properties are obtainable.

It will be understood that the present process may be applied to, fibrous material in conjunction with other substances in addition to the functional agents described above, as for example optical brighteners, stabilizers, softeners, surface active agents, reactive bacteriostats, antistatic and other finishes and the like.

As a further feature of this invention it has been found that the extraordinary rnultiple reactivity of the 2-vinylsulfonylethanol enables the attainment of further unexpected improvements with respect to the permanency of attachment of any of the aforementioned functional agents to the fibrous material. For example, any such functional agent containing any reactive situs such as present in various fibrous materials as described above, if included in the initial treating solution containing the 2-vinylsulfonylethanol, will likewise be the subject of a monofunctional reaction with the latter compound. The resulting functional agent will thereby be similarly substituted in this initial stage by hydroxyethylsulfonylethyl groups. In the subsequent curing step, these initially reacted functional agents will react with the fiber in a manner similar to the above described cross-linking reaction, whereby the functional agent will be permanently fixed to the fiber. By way of example, materials such as polyvinyl alcohol, starch and other finishing agents, or any other functional agent containing reactive groups such as hydroxy, amino, thiol, etc., may be included in the initial treatment medium containing the 2-vinylsulfonylethanol in appropriate amounts sufficient to deposit, for example, about 0.5 to 20% of the agent by weight of the fiber, depending upon the results desired, whereby the above described permanent effects are obtained. It will be understood that in such instances, increased amount of 2 vinylsulfonylethanol should be included in the initial treating solution to compensate for the amounts of such compound reacting with the functional agent. The initial reaction between the functional agent and the 2-vinylsulfonylethanol will usually precede the reaction between the fiber and the 2-vinylsulfonylethanol due to prior inclusion of such agent in the treating solution and/or its greater reactivity with the 2-vinylsulfonylethanol. For similar reason, equivalent results may be obtained by first carrying out the initial reaction between the 2-vinylsulfonylethano1 and the functional agent such as polyvinyl alcohol, starch, etc. in a separate preliminary step and the resulting monofunctionally reacted product applied to the fibrous material as the last wet treatment prior to the curing step. The latter embodiment will of course be necessary if the initially reacted fibrous material is subjected to intermediate wet treatments prior to curing since such treatments would tend to remove the monofunctionally reacted functional agent from the fibrous material before it is fixed to the fiber in the curing step.

The following examples are only illustrative of the present invention and are not to be regarded as limitative. All parts and proportions referred to herein and in the appended claims are by Weight unless otherwise indicated.

EXAMPLE I A length of cotton cloth is padded with the following solution at 80% wet pickup.

2 6.0 parts (34% active)--2-vinylsulfonylethanol 2.0 parts--soda ash 72.0 parts-water The treated fabric is then dried and cured at 360 F. for 1.5 minutes and the cured fabric washed, rinsed and dried. The fabric so produced had excellent dry and wet crease resistance when tested by A.S.T.M. test method D1295-53T.

8 EXAMPLE II A length of cotton cloth is padded with a 25% aqueous solution of 2-vinylsulfonylethanol at 60% wet pickup and then, with or without intermediate drying, padded with a 2% aqueous NaOH solution at pickup, rolled on a stainless steel roller, and the roll covered with polyethylene film to prevent evaporation and allowed to stand for one hour or less. The fabric is then unrolled, rinsed with a 1% aqueous solution of acetic acid to neutralize excess caustic, Washed, rinsed and dried. The resulting cloth exhibits improved wet crease resistance as compared with the untreated fabric. It analyzes at 0.98% sulphur, establishing reaction of the 2-vinylsulfonylethanol with the fabric.

The addition of a salt, as for example 10 to 20% of sodium sulfate, to the above aqueous solution of NaOH is often particularly effective in minimizing stripping of the 2-vinylsulfonylethanol from the fabric.

EXAMPLE III A portion of the fabric produced in Example II is fashioned into a garment having creases, pleats, folds, seams, etc. The garment is then treated in a 2% aqueous solution of sodium carbonate at 100% pickup, ironed with a warm iron to remove wrinkles and dried, and cured in an oven at 360-370 F. for 1.5-2 minutes. The treated garment exhibits excellent dry and wet crease resistance compared to an untreated garment and the creases, pleats and other mechanical deformations are resistant to removal by washing, ironing, dry cleaning, pressing, and other wet and mechanical treatments.

EXAMPLE IV Another portion of the fabric produced in Example II is dyed from an aqueous medium with about 1.25- 1.5% by Weight of the fiber of a direct dye resistant to alkali and peroxide such as Fastusol Red 4BA, Fastusol Orange L7G, Fastusol Turquoise Blue LGA or the like, or other type of dye. The dyed fabric is then padded with a 2% aqueous solution of soda ash at 100% pickup, dried, and heat cured at about 360 F. for 1.5 minutes. The cured fabric is then peroxide bleached, rinsed and dried. The resulting treated fabric exhibits excellent dry and wet crease resistance as well as wash fastness of the dyeing compared to dyed but otherwise untreated fabric.

This invention has been disclosed with respect to certain preferred embodiments and various modifications and variations thereof will become obvious to the person skilled in the art. It is to be understood that such modifications and variations are to be included within the spirit and scope of this invention.

We claim:

1. A stepwise modification of a fibrous material having reactive sites with the difunctional reactant, 2-vinylsulfonylethanol, which comprises a first step of effecting reaction between one functional group of the reactant and an active site of the fibrous material under aqueous alkaline conditions and a second step of effecting reaction between the other functional group of the reactant and an active site of the fibrous material at a temperature of at least 100 C. in the presence of an alkaline catalyst.

2. The modification of claim '1 wherein said fibrous material is cellulose.

3. The modification of claim 1 wherein said alkaline conditions are provided by sodium hydroxide.

4. The modification of claim 1 wherein said alkaline conditions are provided by sodium carbonate.

5. The modification of claim 1 wherein the fibrous material is subjected to a dyeing process between said first and second steps.

6. The modification of claim 1 wherein the fibrous material is subjected to at least one mechanical deformation between said first and second steps.

9 1O 7. Substantially uncross-linked fibrous material con- 2,539,704 1/1951 Schoene. taining at least one reactive site selected from the group 3,106,439 10/ 63 Va consisting of reactive hydrogen and halogen atoms and unsaturated linkages, and chemically combined hy- FOREIGN PATENTS droxyethylenesulfonylethylene groups. 5 625,790 8/1961 Canada.

8. Substantially uncross-linked cellulosic fibrous ma- 607,339 10/1960 Canadaterial containing chemically combined hydroxyethylene- 1,227,317 3/ 1960 France- 1 l l fony ethy eneoxy groups GEORGE F. LESMES, Primary Examiner References Cited 10 J. CANNON, Assistant Examiner UNITED STATES PATENTS U.S. C1. X-R. 2,524,399 10/1950 Schoene et a1. 2243; 8115.5, 115.6, 115.7, 120, 127.5, 128, 129;

3,046,075 7/1962 Kantner et al. 38-144 

